Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
FDN-903 BACKGROUND OF THE INVENTION
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Field of the Invention
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This invention relates to solventless, fast-setting,
anaerobic adhesive composition for bonding together two or
- S more substrates by anaerobic polymerization.
Description of the Prior Art
The phenomenon of anaerobic polymerization is one
that is well known in the art and one which is readily
effected in cormnercial practice by interposing an adhesive
~, ,
10 composition between two opposing substrate surfaces that
are to be bonded together with such adhesive composition.
x Upon such substrate surfaces being pressed together, air
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- is thereby excluded, giving rise to rapid polymerization
''7 of the adhesive composition which, in turn, causes the two
15 substrates to be bonded via the resultant polymerized adhes-
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~- ive composition.
The use of acrylate monomers for this purpose is
well know and described in a number of prior U.S. patents,
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~ ~ such as U.S. 3,419,512, 3,425,988 and 3,435,012. For example,
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U.S. 3,419,~12 disclose~ anaerobic adhesive compositions com-
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1 prising monomers of dimethylacrylate or diacrylate esters
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of polyglycols, an organic peroxide polymerization initiator,
water, an acid or acid salt, and, oprionally, an organic
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FDN-903
tertiary amine and a plasticizer, and teaches that such
~ compositions are capable of attaining a range of specified
"` bond strengths within rapid setting times. U.S.3,425,988
x rel2tes to polyurethane-polyacrylate sealant compositions
; 5 comprising the reaction product of an acrylate ester,
an organic polyisocyanate and a peroxy polymerization
initiator,, which compositions polymerize when placed
between non-porous substrate surfaces.
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~ Previous bonding processes, such as those above,
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i~ 10 that have been characterized by interposing a polymerizable
~"
~ adhesive composition between a plurality of substrates, or
;~ by applying an adhesive composition to the surface of one
substrate and then pressure contacting the resultant
adhe8ive containing substrate surface to a second substrate,
have frequently given rise to inferior products that have
' been characterized by non-uniform bond strength, owing to
.~ slight variations in thickness and the like of the intermed-
~?
iate adhesive layer, or decreased bond strength of the
resultant bonded material over a moderate time span such as
a month. Furthermore, such prior art processes have quite
often required the use of solvents in order to promote bond-
ing or to "activate" the substrate surfaces. Such solvents
have often proved to be undesirable,both from pollution and
fire hazard standpoints, and for use in bonding solvent
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impervious surfaces.
Accordingly,it is an object of the present invention
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to provide new and improved solventless, fast-setting anaerobic adhesive
compositions which are capable of forming high-strength bonds to substrate
surfaces at ambient temperatures.
SUMMARY OF THE INVENTION
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A solventless, fast-setting anaerobic adhesive composition
comprises two monomer parts which are adapted to be copolymerized
anaerobically at ambient temperature between opposing surfaces to form a
high-strength bond thereto. One part comprises a multifunctional acrylate -
monomer and the other an N-vinylamide monomer. The formulation also includes
a redox system consisting of oxidizing and reducing agent components for
initiating polymerization between said monomers. The oxidizing agent of the
i'; redox system may be present in either one of said parts, preferably with
the multifunctional acrylate. The reducing agent is present in the other
part, usually the N-vinylamide Upon anaerobic admixing of the respective
parts of the composition at ambient temperature, the oxitizing and reducing
agents react to generate free radicals which initiates copolymerization of
the monomers to form the desired high-strength adhesive bond to said surfaces.
s .
Accordingly, the present invention provides a solventless, fast-
~ . .
,- setting adhesive composition consisting essentially of two monomer parts
which are adapted to be copolymerized anaerobically at ambient temperature
~i between opposing surfaces to form a high-strength bond thereto, one of said
.....
parts comprising a multi~unctional acrylate monomer and the other part an
'~,5.. , N-vinylamide monomer, one of said parts having an oxidizing agent present
1;~
~` therein and the other part a reducing agent, said agents being capable of
':
reacting when brought together to initiate copolymerization of said monomers
to form said desired bond.
The present invention also provides a method of rapidly forming
~,~ an adhesive bond between two opposing surfaces which comprises the steps of:
;:
a) applying the above formulation to one or both of said surfaces,
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and
b) pressing said surfaces together to cause rapid anaerobic
copolymerization of said monomers to form said desired high-strength adherent
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34'7
bond.
; DESCRIPTION OF THE PREFERRED EMBODIMENTS
: In accortance with the present invention, Part A comprises a
mu:ltifunctional acrylate monomer which has at least two acrylate groups per
molecule, such as a diacrylate
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- FDN-9~3 or a triacrylate. Preferred multifunctional acrylates arethose which are formed by esterification densation of polyols
with acrylic acid. Thus, suitable multifunctional acrylates
include 1,6-hexanediol diacrylate, trimethylolpropane trimeth-
acrylate, diethylene glycol diacrylate, dipropylene glycol
dimethacrylate and diglycerol dimethacrylate.
- Part B of the formulation contains a monomer which
will copolymerize anaerobically with the multifunctional
.;
acrylate component at ambient temperature to form a cross-
linked copolymer of high-strength. In accordance with the
7'. invention, this monomer is an N-vinylamide which polymerizes
; through its ethylenic group. Suitably N-vinylamides include
N-vinyl carboxylic amides and N-vinyl sulfona~ides. Preferred
.,;
N-vinyl carboxylic amides are the ~-vinyl lactams Exemplary
of such N-vinyl lactams are N-vinyl-2-pyrrolidone and its
.'s ~
~. alkylated analogs, such as N-vinyl-5-methyl-2-pyrrolidone,
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; N-vinyl-3, 3-dimethyl-2-pyrrolidone, N-vinyl-2-piperidone,
N-vinyl-6-caprolactam, N-vinyl-hexahydro-phthalamidine, N-
vinyl naphthostyrile and N-vinyl-morpholidone
:
Polymerization between said monomers is initiated
.,
; ~ by a suitable redox system, to be described in detail here-
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after.
In operation, parts A and B are polymerized anaero-
, . ..
~ bically by applying them to one or both opposing surfaces
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~ 25 desired to be bonded together, and pressing the surfaces
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iO~i~47
FDN-903 together, thereby to shut off the supply of air therebetween.
Advantageously, the combination of monomers herein has been
found to copolymerize anaerobically at a rate faster than
either monomer alone. The resultant copolymer forms an
; 5 adherent, high-strength bond to both surfaces.
The redox system which initiates polymerization
between the monomers whe., the parts are admixed anaerobically
~i includes an oxidizing agent and a reducing agent. The
oxidizing agent is present in one part of the formulation,
~rl 10 for example, in part A, and the reducing agent is present
~ç in the other part of the formulation, for example, in part
$!, B. Thereby, upon admixing o the respective parts, the
; oxidizing and reducing agents react to generate free radicals
... . .
which initiates the desired polymerization.
Preferably the oxidizing agent is present in the
acrylate moiety of the formulation and is an organic peroxide
; or an organic hydroperoxide. Suitable organic peroxides for
use herein include diacyl peroxides, such as diacetyl,
- dibenzoyl and dilauroyl peroxide; dialkyl peroxides, such
as di-t-butyl peroxide; and cyclohexene peroxide. Suitable
hydroperoxides include t-butyl hydroperoxide and p-methane
hydroperoxide.
~`~ The reducing agent of the redox system preferably
is present as a component of the N-vinylamide part of the
- 25 formulation. Typical reducing compounds o the invention
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FDN-903 are aliphatic and aromatic amines, including diamines,
triamines, tetramines, etc., including N-alkylated amines,
and metallo-organic compounds. Exemplary of such reducing
agents are triethylenetetramine, N,N-diethylaniline and
cuprous acetonylacetonate.
The oxidizing and reducing agents preferably
should be soluble in their respective parts of the formu-
lation, and also not cause premature polymerization of the
monomer prior to admixing of both parts. Furthermore, it
is also preferable that the oxidizing and reducing agents
be selected as a particularly useul pair for performing
their desired ~unction.
The oxidizing and reducing agents are present in
an amount sufficient to generate the necessary free radicals
to initiate polymerization. Usually about 0.1% to about 5%
by wt. of said part is sufficient, preferably about 2%-3%
by wt.
PREFERRED REDOX SYSTEMS
;:
Oxidizing A~ent Reducing Agent
20Organic hydroperoxide Polyamine-H2N(-C-C-NHn)H n-1-8
t-Butyl hydroperoxide Triethylenetetramine
Organic peroxide N-Alkylated aromatic amine
Benzoyl peroxide N,N-Diethylaniline
Organic hydroperoxide Metallo-organic
; 25Cumene hydroperoxide Cuprous acetonylacetones
In order to provide a more useful formulation for
~- practical application as an adhesive, it may be necessary
lO~lB4~
FDN-903 to adjust the viscosity of each part so as to produce a some-
what viscous liquid which can be applied easily to the sub-
strate surfaces and retained therebetween while polymeriz-
ation occurs. If the monomer themselves are relatively
.viscous, then they may be used-directly. However, if the
monomer is too thin, i.e. a free-flowing liquid, it is
` necessary to add a thickener, that is, a soluble resin which
will increase the viscosity of the monomer, and not inhibit
polymerization. Preferably, it should increase the viscosity
of the monomer to between 50-5000 centipoises. For many
multifunctional acrylate and N-vinylamide monomers, it
i8 necessary to add resin in the amount of between about
5-50~/O by wt of the monomer. Suitable resins include
cellulose acetate polyvinyl acetate, and other well known
resins suitable for this purpose
To effect bonding, there are two preferred modes
of application:
.,r~ (1) applying parts A and B separately to each of
two surfaces to be adhered, and pressing the surfaces toget-
her firmly until the polymerization occurs and the bond
begins to set.
(2) premixing parts A and B on one surface and
-,:
-: .
~hen pressing the second untreated surface on top of the
adhesive-moistened surface. If the mixture of parts A and
B is not too thick e.g. 1.0 mils or less, no reaction or
,...
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1~1847
FDN-903 pre-setting up of the adhesive will occur for some time
since air inhibits polymerization. However, once the
glue is sandwiched between the two materials to be adhered,
air is cut off and consequently, polymerization takes
place.
.
Preferably, parts A and B are admixed so as to
effect copolymerization between the monomers to form a
cross-linked copolymer having about a 1:1 molar ratio of
,
acrylate group to N-vinylamide. The molar equivalent of
an acrylate group is calculated by dividing the molecular
weight o~ the multifunctional acrylate monomer by the
number o acrylate groups present therein, e. g . two,
three, etc. This bond developed with this composition
., ,
is produced within the fastest setting times. However,
other ratios may be used as well, including most suitably
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- an excess of the multifunctional acrylate, preferably up
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to a ratio of about 10:1, which insures that no residual,
, . - . .
`E unpolymerized N-vinylamide will be present after polymeriz-
., ,`,- .
ation. Excess acrylate is desirable since many N-
vinylamides have characteristic odors which would persist
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in the region of the bond. On the other hand, if too
~;~ much acrylate is present, then polymerization will proceed
at a slower rate, and produce a weaker bond. Therefore,
it is more nearly an optimum condition to maintain a slight
excess of acrylate over the 1:1 ratio.
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To improve the bond strength and to speed up the
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lOgi847
FD~-903 polymerization, a quantity of aluminum powder may be added
to either or both parts of the formulation. Generally
about 10% by wt. of aluminum will result in the improve-
ment desired with respect to these parameters.
Generally the setting times of the adhesive com-
position of the invention is less than 60 seconds, and
often as low as 5 seconds. Occasionally, the setting
times may be somewhat longer particularly if the surfaces
to be bonded are rather porous.
The present invention may be illustrated further
by means of the following examples which are not intended
to limit the scope of the invention in any way.
EXAMP~E I
,s The following solutions were made up:
,
~ (Eastman's)
B' Part A: 7 g. EAB-500-5 (cellulose acetate Butyrate)
,, .
93 g. 1, 6-hexanediol diacrylate
~- 3 g. t-butyl hydroperoxide (70% by wt.)
Part B: 7 g. EAB-500-5
93 g. N-vinylpyrrolidone
... .
' 3 g. triethylenetetramine
,
^` One half ml. of Part A was placed on a glass plate;
; 1/2 ml. of Part B was placed on another glass plate. The
two glass plates were pressed together so that the two
components were pushed together to give a thin glue line
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~ 0.3 ml. Within 60 seconds a firm bond resulted.
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iO91~47
FDW-903 EXA~IPLE 2
The following solutions were made up:
Part A: 8 g. EAB-500-5
90 g. 1,6-hexanediol diacrylate
2 g. benzoyl peroxide
Part B: 8 g. EAB-500-5
; 90 g. N-vinylpyrrolidone
~ 2 g. N,N-diethylaniline
.
A 0.3 g. aliquot of Part A was spread evenly over
. 10 1/3 of the top surface of a piece of 1/2" plywood (4" by
1-1/2"). The same operation was performed with Part B on
another piece. The wetted surfaces were brought into firm
contact (about 0.2 lbs/in2 pressure). After 8 min. a firm
,;
bond resulted. The excess glue which was pressed out
remained fluid and could be wiped away to give a neat
appearance. The next day the shear strength of the bond
was found to be 280 lbs/in2.
EXAMPLE 3
~ Part A from Example 1 was spread as a thin film
;, 20 on a latex-pain~ed wall. Part B from Example 1 was spread
.,;,
thinly over a 2" x 2" piece of smooth rigid polyvinyl-
chloride plastic (40 mil thick). The PVC was pressed
against the wall so that the two liquid components came
in contact. After 10 seconds, finger pressure was removed.
Within 60 seconds, the PVC was firmly bonded to the painted
wall.
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FDN-903EXAMPLE 4
The procedure described in Example 2 was repeated
using pieces of rigid PVC 40 mil thick instead of plywood.
The bond was set in about 6 minutes. The next day the
5shear strength was measured on an Instron machine. The
PVC failed before the adhesive bond ruptured.
EXAMPLE 5
The following solutions were made up:
~, B Part A:40 g. Union Carbide, Vinylite AYAC (low
M.W. polyvinyl acetate)
60 g. 1, 6-hexanediol diacrylate
3 g. benzoyl peroxide
~; Part B: 40 g. AYAC
60 g. N-vinylpyrrolidone
3 g. N,N-diethylaniline
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Equal weights of A & B were placed on each of two
glass plates. The plates were pressed together so that
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A & B were squeezed together. The bond set in 25 seconds.
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1847
FDN-903 EXAMPLE 6
The following were made up:
Part A: 7 g. EAB-500-5
93 g. 1,6-hexanediol diacrylate
10 g. ALCAN 5100 aluminum powder
3 g. benzoyl peroxide
Part B: 40 g. AYAC
60 g. N-vinylpyrrolidone
3 g. N,N-diethylaniline
A 3/4" deep hole (5/16" dia.) was drilled into
a brick. A 1/2 mil aliquot of Part A was placed in the
, .
hole followed by 1/2 mil aliquot of Part B. A 4/16" O.D.
' threaded steel bolt was inserted and briefly moved up
and down to mix A & B. After standing 60 seconds, a
- 15 strong bond developed. A 20 lb. pull failed to dislodge
the bolt.
It will be understood that it is intended to cover
all changes and modifications of the examples of the
, ,s
invention herein chosen for the purpose of illustration
which do not constitute departures from the spirit and
scope of the invention.
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